Spontaneous Change, Entropy, and Free Energy

A. SPONTANEOUS PROCESS
Spontaneous process - A physical or chemical change that occurs by itself. A process that takes place without energy from an external Source

Entropy, S - A thermodynamic quantity that is a measure of how spread out or dispersed the energy of a system is among the different possible ways that
system can contain energy
Absolute Entropy - The absolute value of entropy of a substance
Standard entropy, S°- The absolute entropy of a substance at 1 atm and 25 °C
Gibbs Free Energy, G - Energy available to do useful work. Used to express the spontaneity of a reaction more directly
Standard Free Energy, ΔGrxn° - The free energy change for reaction when it occurs under standard state conditions, when reactants in their standard states
are converted into products in their standard states
Equilibrium constant, K - A number equal to the ratio of the equilibrium concentrations of the products to the equilibrium concentrations
of reactants, each raised to the power of their stoichiometric coefficients
State functions - Properties that can be expressed as (final – initial) states
Thermodynamics – the branch of physical science that deals with the relations between heat and other forms of energy (such as mechanical, electrical, or

Properties that can be expressed as (final – initial) and we write with Δ such as ΔE = Ef – Ei are called state functions.
Properties that you cannot calculate by just knowing final and initial states but must know how process occurred are called path functions.

Laws of Thermodynamics
Zeroth Law – “If two bodies are each in thermal equilibrium with some third body, then they are also in equilibrium with each other.” Thermal equilibrium
means that when two bodies are brought into contact with each other and separated by a barrier that is permeable to heat, there will be no transfer of heat
from one to the other.
1st Law - Energy of the universe is constant. “Energy can be converted from one form to another but cannot be created or destroyed.”
2nd Law – Entropy of universe increases. “The entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium
process.”
3rd Law – At absolute zero, the entropy of a perfect crystal is 0. “The entropy of a perfect crystalline substance is zero at the absolute zero of
temperature (T = 0 K= -273.15 oC).”

A spontaneous process is a physical or chemical change that occurs by itself. These processes occur without requiring an outside force and continue until
equilibrium is reached.
In a chemical reaction, ΔHreaction = ∑Hproducts - ∑Hreactants. If it is exothermic, then ΔHreaction = (-). To get a negative ΔHreaction , the Hproducts must be lower than
the Hreactants.
A spontaneous process is one that takes place without energy from an external source. For a chemical reaction to be spontaneous, it should proceed as
written (from left to right), without an input of energy.
Examples of Reactions:
Combustion of methane
CH4 + 2O2 —> 6CO2 + 2H2O ΔHo = - 890.4 kJ/mol
Acid-base neutralization reaction
H+(aq) + OH- (aq) —> H2O (l) ΔHo = - 56.2 kJ/mol
* Both of these reactions are very exothermic and are not reversible.
Solid to liquid phase transition of water
H2O (s) —> H2O (l) ΔHo = 6.01kJ/mol
Dissolution of ammonium nitrate in water
NH4NO3 (s) —> NH4 + (aq) + NO3- (aq) ΔHo = 6.01 kJ/mol
* Ice melting above 0oC and ammonium nitrate dissolving in water are both spontaneous process yet endothermic.

B. ENTROPY

Entropy, S, is a thermodynamic quantity that is a measure of how spread out or dispersed the energy of a system is among the different possible ways that
system can contain energy. It is a quantity that is generally used to describe the course of a process, that is, whether it is a spontaneous process and has a
probability of occurring in a defined direction, or a non-spontaneous process and will not proceed in the defined direction, but in the reverse direction.
• The SI unit of entropy is joules per Kelvin (J/K) and, like enthalpy, is a state function.

Most processes are accompanied by entropy change. The following are processes that lead to an increase in entropy of the system.
Process Order —> Disorder
Melting Solid —> Liquid
Vaporization Liquid —> Vapor
Dissolving Solute —> Solution
Heating System at T1 —> System at T2 (T2 > T1)
The spreading out of more concentrated molecules and the spreading out of more concentrated energy are changes from more order to more random. The
changes that occur are the ones that lead to an increasing randomness of the universe. Entropy is sometimes referred as the measure of randomness and
disorder.

<— heat <— (direction of heat flow)

At high enough temperature, the spontaneous change is from Solid Liquid Gas; gas is more random than liquid and liquid is more random than solid. There
is an increase in entropy (S) of the system by going from solid to liquid to gas.

C. Entropy and the Second Law of Thermodynamics

The Second Law of Thermodynamics deals with entropy. It tells whether a process or chemical reaction can occur. The connection between entropy and the
spontaneity of a reaction is expressed by the second law of thermodynamics: It states that: “The entropy of the universe increases in a spontaneous process
and remains unchanged in an equilibrium process.”
Because the universe is made up of the system and the surroundings, the entropy change in the universe (ΔSuniv) for any process is the sum of the entropy
changes in the system (ΔSsys) and in the surroundings ΔSsur).
ΔSuniv = ΔSsys + ΔSsur > 0 Process is spontaneous.
ΔSuniv = ΔSsys + ΔSsur = 0 Process tends not to occur; equilibrium is attained.
ΔSuniv = ΔSsys + ΔSsur < 0 Reverse process occurs spontaneously.

Calculating Entropy Changes in the System: Standard Entropy of Reaction, ΔS° rxn
How is entropy change determined? What data are needed for the calculation?
Suppose that the system is represented by the following reaction: aA + bB —> cC + dD
As in the case for the enthalpy of a reaction, the standard entropy of reaction ΔS° rxn is given by the difference in standard entropies between the products
and the reactants.
ΔS° = ΣnS° (products) − ΣmS° (reactants)
• Where m and n are the stoichiometric coefficients in the reaction.
ΔS° rxn = [cSo (C) + d So (D)] ‒ [aSo (A) + bSo (B)]
The standard entropy values of compounds have been measured in J/K mol. To calculate the ΔS° rxn (which is the ΔSsys), the values may be found in the
Thermodynamic Data Table. Thermodynamic tables have absolute entropy of substances at 25°C and 1atm.
• Remember, the greater the value of ΔS then the greater is the increase in the randomness of the system.

General rules for predicting entropy change of the system:

1. If the reaction produces more gas molecules than it consumes, ΔS° is positive.
2. If the total number of gas molecules diminishes, ΔS° is negative.
3. If there is no net change in the total number of gas molecules, ΔS° may be positive or negative, but will be relatively small numerically.
Practice Problem 1:
Predict whether the entropy change of the system in each of the following is positive or negative.
O2(g) —> 2O(g)
N2 (g, 10 atm) —> N2 (g, 1atm).
6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g).
2 H2 (g) + O2 (g) —> 2 H2O (l)
NH4Cl (s) —> NH3(g) + HCl (g)

Practice Problem 2:
Calculate S at 25C for the reduction of given these absolute entropies: 2PbO(s) + C(s) —> 2Pb(s) + CO2(g)

Calculating the Entropy Changes in the Surroundings, ΔSsur

For constant-pressure process the heat change is equal to the enthalpy change of the system ΔH sys,. Then the change in entropy of the surroundings ΔSsurr
is proportional to the ΔHsys. ΔSsurr —> − ΔHsys
The minus sign is used because, if the process is exothermic, ΔH sys is negative and the ΔSsurr is a positive quantity, indicating an increase in entropy.
For an endothermic process, ΔHsys is positive and the negative sign ensures that the entropy of the surroundings ΔHsurr decreases. The change in entropy
for a given amount of heat absorbed also depends on the temperature.

• If the temperature of the surroundings is high, the molecules are already quite energetic. Therefore, the absorption of heat from an exothermic process in
the system will have relatively little impact on the motion of the molecules and the resulting increase in entropy of the surroundings will be small.
• However, if the temperature of the surroundings is low, then the addition of the same amount of heat will cause a more drastic increase in molecular
motion and hence a larger increase in entropy. ΔSsurr = −ΔHsys/T
Sample Problem 3:
Applying the procedure for calculating the ΔSsys and ΔSsurr to the synthesis of ammonia: Is the reaction spontaneous at 25°C?
N2 (g) + 3 H2 (g) —> 2 NH3 (g) ΔH°rxn = - 92.6 kJ/mol

The Third Law of Thermodynamics and Absolute Entropy

The Third Law of Thermodynamics states: “The entropy of a perfect crystalline substance is zero at the absolute zero of temperature.”

• At absolute zero (T = 0 K= -273.15 oC), the entropy of a perfect crystal is 0.

• As the temperature increases, the freedom of motion increases. The entropy of any substance at a temperature above 0 K is greater than zero.
• A solid like glass with imperfections built into it will not have entropy = 0 even at 0 K because it is not a perfect crystal and still has some randomness left in
it.
At absolute zero, all atomic motion stops. Atoms and molecules are no longer vibrating around or moving past each other. However, it becomes harder and
harder to lower the temperature as you get closer and closer to absolute zero. But even though scientists are not able to attain the T = 0 K, it is still a useful
reference point.
Absolute Entropies
The reference point for entropy of a substance is entropy at 0 K. Entropy increases as temperature increases creating more randomness. The lowest
entropy, therefore, occurs at this temperature (S = 0 J/ K mol at T = 0 K).
Thermodynamic tables may have absolute entropy of substances at 25°C and 1atm. But the reference point is S= 0 J/K for 1 mol of substance at 0 K.
• If the ΔHf ° for an element is 0 at the standard state of 25°C and 1 atm, the S° for an element is not equal to 0 at 25°C and 1 atm. (The symbol ° is used to
indicate the standard state of 25oC and 1 atm.)
• If the ΔHf ° for a compound is based on its formation from its elements, the S° for a compound is not based on its formation from its elements. Entropy will
be 0 only at -273.15 oC not at 25oC. If the entropy of a pure element is not zero at standard state, it cannot be assumed as zero; its value has to be
determined. The absolute entropies could be used to calculate ΔS entropy change for a reaction.

D. Gibbs Free Energy, G

Another thermodynamic function is used in order to express the spontaneity of a reaction more directly. This is called Gibbs free energy, G. The use of G
predicts changes that are focused on the system. Gibbs free energy is defined as: G = H – TS
• All the quantities in the equation pertain to the system; the temperature T is the temperature of the system.
• G has units of energy; both H and TS are in energy units.
• H, S and G are all state functions.
If the entropy of the universe increases then the ΔG of the system will decrease. The direction of spontaneous change is negative ΔG for system. The ΔG
tells us if a change can occur for a chemical reaction.
If ΔSuniv is (+) for universe then ΔG for system is ( - ). The ΔG for the system is a convenient way to predict a change.
ΔSuniv ΔG ΔSuniv Reaction
+ - Increase Spontaneous, will go
0 0 Stay the same No change at equilibrium
- + Decrease Not spontaneous, will not go, the reverse will

Determining spontaneity of a reaction using ΔG

The change in free energy (ΔG) of a system for a constant-temperature process is ΔG = ΔH –TΔS
In this context, free energy is the energy available to do work. If a particular reaction is accompanied by a release of usable energy (ΔG is negative), the
reaction is spontaneous.
• Unless stated otherwise, the ΔH, ΔS and ΔG refer to the system at 25 oC. Most of our calculations are for values of ΔG at 25oC (298 K).

Summary of conditions for spontaneity and equilibrium at constant temperature and pressure in terms of ΔG

ΔG < 0 The reaction is spontaneous in the forward direction.

ΔG > 0 The reaction is nonspontaneous. The reaction is spontaneous in the opposite direction.
ΔG = 0 The system is at equilibrium. There is no net change.

Methods to determine change in Gibbs Free Energy (ΔG)

• Determining ΔG using ΔH and ΔS data.
How is Gibbs free energy change determined when ΔH and ΔS are available? ΔG = ΔH –TΔS

Sample Problem 3:
The old camera flash bulb used Mg metal sealed in a bulb with oxygen. The reaction is: Mg(s) + ½ O2(g) —> MgO(s)

Practice Problem 4:
Ozone (O3) in the atmosphere can react with nitric oxide (NO): O3(g) + NO(g) —> NO2(g) + O2(g).
• Calculating ΔG from Standard Free Energies

If the data for ΔG of formation ΔGf° of the reactants and products are available, the following equation is used.
ΔG° = Σ nΔGf° (products) − Σ mΔGf° (reactants)
• Where m and n are the stoichiometric coefficients in the reaction and ΔG f° is the standard free energy of formation ΔGf° is the standard free energy of
formation at 25 °C and 1atm for 1 mol of compound formed from its elements. The ΔGf° can be used to get the ΔG of a reaction just like using ΔH f° to get
ΔH for reaction. The standard free energy ΔG° of element in the standard state is 0.

Factors affecting the sign of ΔG

In order to predict the sign of ΔG according to the equation: ΔG = ΔH- TΔS, we need to know both ΔH and ΔS. Temperature may also influence the
direction of the spontaneous reaction. The four possible combinations are shown below.
ΔH TΔS ΔG Effects
‒ + ‒ Reaction proceeds spontaneously at all temperatures
Example: 2 H2O2 (aq) —> 2 H2O (l) + O2 (g)
+ ‒ + Reaction is spontaneous in the reverse direction at all temperatures
Example: 3 O2 (g) —> 2 O3 (g)

+ + ? Reaction proceeds spontaneously at high temperatures. At low temperatures, the

reverse reaction becomes spontaneous.
Example: 2 HgO (s) —> 2 Hg (l) + H2O (g)
‒ ‒ ? Reaction proceeds spontaneously at low temperatures. At high temperatures, the
reverse reaction becomes spontaneous.
Example: NH3 (g) + HCl (g) —> NH4Cl (s)
Sample Problem Application:
Should you invest in an engine that is said to burn air at room temperature? You are told that a special chamber allows O2 to combine with N2 to form NO2
(nitrogen dioxide) using reaction: ½ N2(g) + O2 (g) —> NO2(g)
Evaluate using thermodynamics ½ N2(g) + O2 (g) —> NO2(g)

Effect of Temperature Effect on Chemical Reactions

The ΔG can be found for different temperature values. ΔG = ΔH – TΔS

The values for ΔS° from S° and ΔH° from ΔHf° can be derived from the Thermodynamic Data Table for both reactants and products at 25 oC and 1 atm. ΔH
and ΔS will vary with temperature but the variation is frequently small. In the calculations, it will be assumed that there is no variation in ΔH or ΔS but only in
T and ΔG.
Determining temperature when a reaction can occur.

Calcium oxide (CaO), also called quicklime is prepared by decomposing limestone (CaCO 3) in a kiln at high temperature and the reaction proceeds as:
CaCO3 (s) → CaO (s) + CO2 (g)
It is a reversible reaction, where CaO readily combines with CO 2 to for CaCO3. To promote the formation of CaO, CO2 is constantly removed from the kiln to
shift the equilibrium from left to right.

Sample Problem 5:
The important determination for the decomposition process to occur is the temperature that will promote the forward reaction. Here we can use the
thermodynamics data for the standard states of the reactants and products at 25 °C.
CaCO3 (s) → CaO (s) + CO2 (g)

Sample Problem 6:
Given: ΔH°= +177kJ and ΔS°= +285J/K for the reaction: NH4Cl(s) —> NH3 (g) + HCl (g)
Find the ΔG° at 25°C and ΔG at 500 °C.

Free energy and Chemical Equilibrium: Relating ΔG° to the Equilibrium Constant
How is free energy change in non-standard states (ΔG) related to the standard free energy change (ΔG°)?
The free energy change when reactants are in non-standard states (other than 1 atm pressure or 1 M) is related to the standard free energy change, ΔG°,
by the following equation. ΔG = ΔG° + RT ln Q
• Here Q is the thermodynamic form of the reaction quotient.
ΔG represents an instantaneous change in free energy at some point in the reaction approaching equilibrium. At equilibrium, ΔG=0 and the reaction
quotient Q becomes the equilibrium constant K.

How does the standard free energy change (ΔG°) relate to the equilibrium constant (K)?
• At equilibrium, ΔG=0 and the reaction quotient Q becomes the equilibrium constant K. 0 = ΔG° + RT ln K
This result easily rearranges to give the basic equation relating the standard free-energy change to the equilibrium constant. ΔG° = −RT ln K
• When K > 1 , the ln K is positive and ΔG° is negative.
• When K < 1 , the ln K is negative and ΔG° is positive.

Sample Problem 6:
Find the value for the equilibrium constant, K, at 25 °C (298 K) for the following reaction. The standard free energy change, ΔG°, at 25 °C equals –13.6 kJ.
2NH3 (g) + CO2 (g) ↔ NH2CONH2 (aq) + H2O(l)

Rearrange the equation: ΔG° = −RT ln K to give equation: ln K = ΔG°

− RT